Thermofluid printing inks and vehicles therefor



' tionable penetration into that-the print be even and sufficiently hard and printing of newspapers Patented Nov. 7, 1944 y ED -Ares PATEN T orrlcs THERMOFLUIDPRINTING ms AND VEHICLES 'rnmsr'on Lothian M. Burgess, Chatham N. .L, assignor to J. M. Huber, tion of New Jersey 11 Claims.

Inc., New York, N. Y a corpora- Drawing.- Application July 8, 1941,

- Serial No. 401.523

movements in. normally. solid, thermo-fluid the ink films freeze immediately to form dry prints adhering to the surface of the stock.

This invention is an improvement or modification of the disclosure in the co-pending application of myself and others, for Printing ink for which United States Letters Patent No. 2,268,595

' 'were issued on January 6, 1942.

Thermo-fluid printing inks must consist of pigments or other suitable coloring .material dispersed in normally solid vehicles which will impart the required physical qualities to the inks. Among the requirements which enter into commercial Cold Set printing work are that the molten ink have, a satisfactory fluidity, body,

tack and cohesiveness for. distribution on the press and for printing at elevated temperatures, that it set quickly when printed, before objecthe paper stock,.and

' 'Cold'Set printing.

free from tack to resist abrasion, smudging or other damage during f 'her printing operations or during the normaluseof the printed matter. These requirements are accentuated in the color and trapping, or superimposing, satisfactorily ii to be used in process," printing, and that'the ink vehicles with the various colored inks. I

Many ofthe thermo-fluid inks heretofore used or multi-color, be compatible successfully for .high speed newspaper printing I or'the like have contained substantial proportions of gilsonite. Gilsonite is a hard bituminous resin of dark brown or black color that imparts,

desirable printing qualities to the, molten' inks, particularly when used with substantial proporaccording to the fCold pigments used in compounding or other printed matter .30

wherein, in addition, the have an exceptionally high fluidity at tions of hard thermo-plastic resins, such as cumarone resins and hardened rosins or rosin' derivatives, which in contrast to the length or stringiness of molten gilsonite are comparatively short" when molten. When gilsonite is so used in colored inks, however, its natural dark color debases the color values of bright pigments and causes the printed ink to have a dull 0r muddy.

tone. Colored thermofiuid inks containing substantial amounts of gilsonitetherefore-are not suitable either for the printing of bright colors or for multi-color printing work.

Itis accordingly the principal object of my invention to provide improved thermo-fluid printing inks which are bright in color, which have printing qualitiesand other physical qualities satisfactory for. high speed commercial printing work, and which are low enough in cost to be used for colo printing in large volume. Another object of my invention is to provide thermo-fluid printing inks which have color qualities, printing-qualities and trapping qualities rendering them suitable A further object of the invention is to provide light-colored or pale thermo-fluid ink vehicles which possess physical andchemical qualities rendering them valuable for use in the compounding of variously colored thermo-fluid printing inks comprising various types of pigments.

According to the present invention, I have found that the foregoing and other desirable objects and advantages may be attained by compounding thermo fluid ink vehicles, and from them improved inks, with a special hard thermoplastic resin base which contains a substantial proportion of a phenolic-modified natural resin or natural resin ester, by which I mean a natural resin or an este thereof that has been reacted with or modified. by phenol-aldehyde resin.

The most common natural resins and natural "resin esters available for modification and and-polyglycol, also may be employed. These pursuant hereto are rosin and copal and-the respective glycerol esters, namely, ester gum and copal ester. Esters of rosin and copal with other polyhydric alcohols, such as polyglycerol, glycol resins and estersmay be modified by phenolaldehyde resins in several known .ways so as to obtain products which remain permanently for use in multi-color' product of the reaction between a phenol and an aldehyde; or'a phenol and an aldehyde may be reacted in the presenceof the resin or ester; or a natural resin may be reacted with a phenol aldehyde resin, during or after which the product of that reaction may be esterified with a polyhydric alcohol, such as glycerol, as disclosed in United States Patents Nos. 1,623,901, 1,800,295 and I have found that such phenolic-modified products, and especially the products of reactions between natural resins, glycerol and heat-com vertible phenol-formaldehyde resins, contribute a' desirable quality of "length or. stringiness to molten thermo-iiuid printing inks, and that valuable inks may be obtained by using such products in combination with comparatively short" hard thermo-plastic resins, such as cumarone 5 resins, hardened rosins and rosin derivatives. Furthermore, thermo-fiuid ink vehicles made with this'resin combination as herein disclosed have a light color and other physical and chemical qualities which permit them to be com- The physical qualities of the resulting inks, both 85 at ordinary temperatures and at elevated printing temperatures, make them particularly useful ,in'high speed letter-press printing by the Cold Set process, as in the printing of newspapers,

magazines and the like. In addition, these inks 40 may have color and trapping qualities suitable for multi-color printing; and they are compatible with most of the pigments employed in colored The phenolic-modified resin constituent of my inlm and vehicles may be procured commercially in prepared. form or may be prepared fromreadily available substances prior to or in the course of compounding the new inks. An example of a suitable commercial product is a product of Reichold Chemicals, Inc., known as Beckopol," which is a phenolic-modified copal ester. A suitable product may be. prepared, for

example, by'heating a natural resin or an ester thereof, such as Ester Gum #125," a glycerol ester of rosin produced by American Cyanamid Company, with a smaller amount of an oil-soluble, heat-convertible phenol-formaldehyde resin such as Super-Beckacite 1001, another product of Reichold' Chemicals, Inc. When following this particular example the heating usually is carried out slowly to about 450 F., until foaming has substantially ceased. The t rmo-fluid ink vehicles of this invention general are made from a special resin combination as aforesaid, wherein the content of comparatiyely short resin predominates over the content of-phenolic-modifled resin,'together with a substantial proportion of hardwaxy material.

waxy material may be natural wax or a synthetic wax or wax substitute; or both waxes and wax substitutes may be used. Suitable natural waxes are carnauba wax, \candelilla wax,

V waxes. tutes are normally solid hydrogenated-oils, such as hydrogenated soya bean oil, and hard waxy For example, the natural resin or ester may be reacted with the resinous Suitable synthetic waxes or wax substireaction products of alkylolamines and substantially saturated hydroxy fatty acids, of which a product of National Oil Products Company, known as "DB1" wax, is an example.

If desired, the vehicle may-contain other organic plasticizing material, suchas certain vegetable or mineral oils, soft or liquid resins, lithovarnish or the like, to impart desirable physical qualities to the molten ink and to serve in part as a substitute for waxy material; but such liquid or oily materials should be used only in a minor proportion, generally of less than 30%,that' is insuflicient to cause objectionable tack or stickiness in the ink at normal temperatures. In many cases it is advantageous to include in the vehicle a small amount, say about 1 to 5%, of a substance such as zinc resinate, zinc or lead naphthanate, lecithin or the like to improve the printing qualitles of the molten ink, as set forth more particularly in a co-pending application of "Jesse K. Boggs and myself, filed April 24, 1941, now United States Patent No. 2,361,740.

The inks embodying this invention which seem to have the most desirable compositions and characteristics hereof are those made with vehicles containing about 20 to of the comsmaller proportion between about 5 and 35% of the phenolic-modified resin. with this resin base there is included a substantial proportion, but usually not more than about 50%. of hard waxy material, When an oily or liquid plasticizing material also is used the content thereof is kept below 30%, and with a comparatively large content of suchmaterial only a small proportion of wax' or other waxy material need be present.

In compounding the new inks, for example, the vehicle is first prepared by melting and mixing the ingredients in a suitably heated container, followed by stirring in of the coloring material, including any fillers, and then by repeated grinding. when theink has been thoroughly ground, it is poured into containers or molds and allowed to cooL- If the phenolic-modified natural resin or ester is to be prepared in conjunction with the compounding of the ink,-this preferably is carerol, glycol and polyglycol.

The proportions of vehicle and coloring material to be used in compounding the inks vary with different vehicle formulae and with different pigments and colors, as will be readily understood in the art. Likewise, there maybe variations in the composition of a given basic vehicle when the same vehicle is used with difierent pigments to produce inks of several different colors or color tones. Such variations, however, need not be great, and they may be effected readily by adding a small amount of an appropriate ingredient or ingredients to the basic vehicle during the compounding of any particular ink therefrom.

Following are examples of useful compositions Montan wax and certain high melting paraffin v embodying my invention:

- Vehicle! Ink III-B, bright yellow Parts by weight Parts'by weight Limedros 40.5 Cumar V 2%. 21 N wood rosin, reacted with.. 24.0 Beckopol 140 '7 Superbeckacite 1001 7.5 5 Hydrogenated soya bean .oil. 30 Cotton seed oil ..i'.'. 25.5 DBI wax; 91 C p a r Paraflln we 3.0 Chrome yellow -s 40 r 100.5 m 0 Ink I-A-bright red Ink III-C, bright blue Parts by weight Parts by weight Vehicle T A 100.5 Cumar V 2%" 24 "Surtex" filler (calcium carbonate or low Beckopol 1 oil adsorption) 1.0 Hydrogenated soya bean'oil 40 mthol Rad 8.0 DBI wax, 91 v 5 a Sur1ex" filler (calcium carbonate of low g 115.5 oil adsorption) -4 5 Four-color process were made as follows: zfii'gg i fi Vehicle II a 4 Parts by weight v n Cumar W Thus, the present invention provides not only Ester gum #125, "reactedwithu; 14.! 25 new bright colored thermo-fluid printing inks and perbec acite colored inks suitable for multi-color printing, but Carnauba wa 20 also light-colored or pale thermo-fiuid ink ve- Litho oil hicles which are well suited for the compounding of ink oi! almost any color. The physical qualiv 93 o ties of these inks 1ahnd vehicles make them especially useful for gh speed letter-press print- Ink mellow ing according to the "Cold Set process.

' Parts by weight The new inks generally are free from volatile Vehicle 71 g g 92 solvents, thermo-setting qualities or other unzmc naphthenate 2 stable material such as would cause them to Hausa yellow 10 change materially inconsistency and printing qualities'under the conditions encountered in v 104 their'luse on a printing press. It will be under- Ink II- B, red stood, however, that small proportions of such 40 materials might be included in the ink for spe- Vehicle T gg cifail7 13111510888 1ilwhile still utilizing the new featureso s, ven on; l lflfl e fil bean on. '7' 3 It also will be evident that the various details,

ingredients and proportions referred to herein- 103 above'm'ay be varied within the scope of the appended claims without departing from my inven- Ink tion, and I therefore desire that-the invention Parts by'weight be accorded a scope commensurate with its con-. Vehicle TT 75 tributigns to the art. as limited only by the fair Peacock Blue 25 requirements of the claims.

I claim: 100 1. A normally solid thermo-fluid printing ink comprising coloring matter incorporated in a Ink H 'f vehicle made with a .resin base which consists Parts b weight substantially entirely of hard thermo-plastic Vehicle TT 92 product of reactions between a phenol an aide- Hydrogenated $0178 5 hyde, and a resin from the'group consisting of Zinc naphthena 2 thermo-plastic natural resins and their poly- Carbon black and toners hydric alcohol esters, together with a larger proo0 portion of hard thermo-plastic resin from, the 123 group consisting of cumarone resins and hard vBright q /yn' and blue mks were made thermoplastic rosin derivatives which contain follows: v r the rosin nucleus. 7 v I q H A M 2. A normally solid thermo-fluid printing ink 9 t ed comprising coloring matter incorporated, in a- Parts by weight light-colored vehicle which contains a hard thencu r V 2 26 moplastic resin base composed substantially en- Beckopol 1400 10 tirely of thermo-plastic natural resin ester re- Hydrogenated soya bean oil. ("Hisor") 42 acted with phenol-formaldehyde resin and a pre- DBI wax, m. p. 91 C 5 ponderant proportion ,of hard thermo-plastic- Zinc resinate v 2 resin from the group consisting of cumarone Strontium lithol red; 11 resins and hard thermoplastic rosin derivatives chrome orango 5 Y which contain the rosin nucleus.

, I 3. A light-col red normally solid thermo-fluid printing ink vehicle having a hard resin base composed substantially entirely oi: a thermoplastic product of the reaction between ester gum and a smaller amount of heat-convertible phenol-formaldehyde resin, together with a preponderant proportion of hard thermo-plastic cumarone resin.

8. A thermo-fluid printing ink comprising coloring material incorporated in a normally solid light-colored vehicle containing about 20 to 4. A light-colored normally solid therma -fluid 50% of resin from the group consisting of hard thermo-plastic cumarones and rosin derivatives which contain the rosin nucleus, about 5 to 35% of a hard thermo-plastic product of the reaction between a glycerol ester of natural resin and heat-convertible phenol-formaldehyde resin, and most of the remainder hard waxy material.

9. A thermo-fluid printing ink comprising coloring matter incorporated in a normally solid light-colored vehicle consisting substantially entirely of about 20 to 50% of resin from the group consisting of hard thermo-plastic cumarones and rosin derivatives which contain the rosin nucleus,

a smaller proportion between about 5 and 35% a thermo-plastic product of reactions between thermo-plastic natural resin, glycerol and heatconvertible phenol aldehyde resin, and more than half of said resins being hard thermo-plastic resin from the group consisting of hard thermoplastic cumarone resins and rosin derivatives which contain the main nucleus.

6. A normally solid thermo-fluid printing having a vehicle which consists almost entirely of hard thermo-plastic resins and hard waxy material as described in claim 5, together with a substantial proportion butless than of non-volatile, liquid, organic plasticizing material.

7. A thermo-fiuid printing inl; comprising coloring material incorporated in a normally solid light-colored vehicle containing about 20 to 50% of resin from the group consisting of hard .thermo-plastic cumarones and rosin derivatives which contain the rosin nucleus and a smaller proportion between about 5 and or a hard thermo-plastic product of the reaction between a glycerol ester oi natural resin and a heatconvertible phenol-formaldehyde resin.

of a hard thermo-plastic product of the reaction between a glycerol ester of, natural resin and heat-convertible phenol-formaldehyde resin, a substantial proportion but less than 30% of liquid organic plasticizing' material and a substantial proportion of hard waxy material.

-l0. A thermo-fluid printing ink comprising coloring matter incorporated in a normally solid light-colored vehicle consisting almost entirely of about 20 to40% of hard thermo-plastic cumarone resin, 9. smaller proportion between about 10 and 30% ot a hard thermo-plastic prodnot of the reaction between a glycerol ester oi natural resin and heat-convertible phenolformaldehyde resin, about 40 to of hydrogenated soya bean oil, and a small amount oi other hard waxy material.

11. A normally solid printing ink comprising coloring matter incorporated in a vehicle having a hard resin base composed substantially entirely oia hard thermo-plastic product of reactions between a phenol, an' aldehyde and a resin 40 from the group consisting of therrno-plastic natural resins and their polyhydric alcohol esters together with 'a preponderant proportion of a hardened rosin.

LO'I'HIAN M. BURGESS. 

